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Fluorescent molecular rotors based on the BODIPY motif: effect of remote substituents

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Abstract

The ability of an unconstrained boron dipyrromethene dye to report on changes in local viscosity is improved by appending a single aryl ring at the lower rim of the dipyrrin core. Recovering the symmetry by attaching an identical aryl ring on the opposite side of the lower rim greatly diminishes the sensory activity, as does blocking rotation of the meso-aryl group. On the basis of viscosity- and temperature-dependence studies, together with quantum chemical calculations, it is proposed that a single aryl ring at the 3-position extends the molecular surface area that undergoes structural distortion during internal rotation. The substitution pattern at the lower rim also affects the harmonic frequencies at the bottom of the potential well and at the top of the barrier. These effects can be correlated with the separation of the H1,H7 hydrogen atoms.

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References

  1. M. A. Haidekker, E. A. Theodorakis, Environment-sensitive Behavior of Fluorescent Molecular Rotors, J. Biol. Eng., 2010, 4, 11–25.

    Article  Google Scholar 

  2. W. R. Browne, B. L. Feringa, Making Molecular Machines Work, Nat. Technol., 2006, 1, 25–35.

    CAS  Google Scholar 

  3. N. Koumura, R. W. J. Nijlstra, R. A. van Delden, N. Harada, B. L. Feringa, Light-driven Monodirectional Molecular Rotors, Nature, 1999, 401, 152–155.

    Article  CAS  Google Scholar 

  4. M. A. Haidekker, W. Akers, D. Lichlyter, T. P. Brady, E. A. Theodorakis, Sensing of Flow and Shear Stress using Fluorescent Molecular Rotors, Sensor Lett., 2005, 3, 42–48.

    Article  CAS  Google Scholar 

  5. R. M. Yusop, A. Unciti-Broceta, M. Bradley, A Highly Sensitive Fluorescent Viscosity Sensor, Bioorg. Med. Chem. Lett., 2012, 22, 5780–5783.

    Article  CAS  Google Scholar 

  6. K. Gawala, W. D. Sasikala, A. Sengupta, S. A. Dalvi, A. Mukherjee, P. Hazra, Modulation of Excimer Formation of 9-(Dicyanovinyl)-Julolidene by the Macroscopic Host, Phys. Chem. Chem. Phys., 2013, 15, 330–340.

    Article  Google Scholar 

  7. M. D’Amico, G. Schiro, A. Cupane, L. D’Alfonso, M. Leone, V. Militello, V. Vetri, High Fluorescence of Thioflavin T Confined in Mesoporous Silica Xerogels, Langmuir, 2013, 29, 10238–10246.

    Article  Google Scholar 

  8. G. Ulrich, R. Ziessel, A. Harriman, The Chemistry of Fluorescent BODIPY Dyes: Versatility Unsurpassed, Angew. Chem., Int. Ed., 2008, 47, 1184–1201.

    Article  CAS  Google Scholar 

  9. M. K. Kuimova, G. Yahioglu, J. A. Levitt, K. Suhling, Molecular Rotor Measures Viscosity of Live Cells via Fluorescence Lifetime Imaging, J. Am. Chem. Soc., 2008, 130, 6672–6673.

    Article  CAS  Google Scholar 

  10. M. A. H. Alamiry, A. C. Benniston, G. Copley, K. J. Elliott, A. Harriman, B. Stewart, Y.-G. Zhi, A Molecular Rotor Based on an Unhindered Boron Dipyrromethene (Bodipy) Dye, Chem. Mater., 2008, 20, 4024–4032.

    Article  CAS  Google Scholar 

  11. J. A. Levitt, M. K. Kuimova, G. Yahioglu, P.-H. Chung, K. Suhling, D. Phillips, Membrane-bound Molecular Rotors Measure Viscosity in Live Cells via Fluorescence Lifetime Imaging, J. Phys. Chem. C, 2009, 113, 11634–11642.

    Article  CAS  Google Scholar 

  12. A. C. Benniston, A. Harriman, V. L. Whittle, M. Zelzer, Molecular Rotors Based on the Boron Dipyrromethene Fluorophore, Eur. J. Org. Chem., 2010, 523–530.

    Google Scholar 

  13. M. A. H. Alamiry, E. Bahaidarah, A. Harriman, T. Bura, R. Ziessel, Fluorescent Molecular Rotors under Pressure: Synergistic Effects of an Inert Polymer, RSC Adv., 2012, 2, 9851–9859.

    Article  CAS  Google Scholar 

  14. N. A. Hosny, G. Mohamedi, P. Rademeyer, J. Owen, Y. Wu, M.-X. Tang, R. J. Eckersley, E. Stride, M. K. Kuimova, Mapping Microbubble Viscosity using Fluorescence Lifetime Imaging of Molecular Rotors, Proc. Natl. Acad. Sci. U. S. A., 2013, 110, 9225–9230.

    Article  CAS  Google Scholar 

  15. P. Loison, N. A. Hosny, P. Gervais, D. Champion, M. K. Kuimova, J.-M. Perrier-Cornet, Direct Investigation of Viscosity of an Atypical Inner Membrane of Bacillus Spores: A molecular Rotor/FLIM Study, Biochim. Biophys. Acta, 2013, 1828, 2436–2443.

    Article  CAS  Google Scholar 

  16. H. Zhu, J. Fan, M. Li, J. Cao, J. Wang, X. Peng, A “Distorted-BODIPY”-based Fluorescent Probe for Imaging of Cellular Viscosity in Live Cells, Chem. - Eur. J., 2014, 20, 4691–4696.

    Article  CAS  Google Scholar 

  17. H. L. Kee, C. Kirmaier, L. Yu, P. Thamyongkit, W. J. Youngblood, M. E. Calder, L. Ramos, B. C. Noll, D. F. Bocian, W. R. Scheidt, R. R. Birge, J. S. Lindsey, D. Holten, Structural Control of the Photodynamics of Boron-Dipyrrin Complexes, J. Phys. Chem. B, 2005, 109, 20433–20443.

    Article  CAS  Google Scholar 

  18. S. Rihn, P. Retailleau, N. Bugsaliewicz, A. de Nicola, R. Ziessel, Versatile Synthetic Methods for the Engineering of Thiophene-Substituted BODIPY Dyes, Tetrahedron Lett., 2009, 50, 7008–7013.

    Article  CAS  Google Scholar 

  19. A. Poirel, A. de Nicola, P. Retailleau, R. Ziessel, Oxidative Coupling of 1,7,8-Unsubstituted BODIPYs: Synthesis and Electrochemical and Spectroscopic Properties, J. Org. Chem., 2012, 77, 7512–7525.

    Article  CAS  Google Scholar 

  20. S. J. Strickler, R. A. Berg, Relationship between Absorption Intensity and Fluorescence Lifetime of Molecules, J. Chem. Phys., 1962, 37, 814–822.

    Article  CAS  Google Scholar 

  21. S. P. Velsko, G. R. Fleming, Solvent Influence on Photochemical Isomerizations - Photophysics of DODCI, Chem. Phys., 1982, 65, 59–70.

    Article  CAS  Google Scholar 

  22. B. D. Allen, A. C. Benniston, A. Harriman, S. A. Rostron, C. F. Yu, The Photophysical Properties of a Julolidene-based Molecular Rotor, Phys. Chem. Chem. Phys., 2005, 7, 3035–3040.

    Article  CAS  Google Scholar 

  23. P. D. Zoon, A. M. Brouwer, A Push-Pull Aromatic Chromophore with a Touch of Merocyanine, Photochem. Photobiol. Sci., 2009, 8, 345–353.

    Article  CAS  Google Scholar 

  24. The term B-C8-CT refers to the angle tended by the boron atom, the meso-carbon atom and the carbon atom of the para-methyl group on the tolyl group (for BOD this latter atom is replaced with the para-hydrogen atom).

  25. D. Ben-Motz, C. B. Harris, Torsional Dynamics of Molecules on Barrierless Potentials in Liquids. II. Test of Theoretical Models, J. Chem. Phys., 1987, 86, 5433–5440.

    Article  Google Scholar 

  26. B. G. Levine, T. J. Martinez, Isomerization Through Conical Intersections, Annu. Rev. Phys. Chem., 2007, 58, 613–634.

    Article  CAS  Google Scholar 

  27. Calculated as the difference between the two C8-B-F bond angles.

  28. S. P. Velsko, D. H. Waldeck, G. R. Fleming, Breakdown of Kramers Theory Description of Photochemical Isomerization and the Possible Involvement of Frequency Dependent Friction, J. Chem. Phys., 1983, 78, 249–258.

    Article  CAS  Google Scholar 

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Author notes

  1. Sandra Rihn

    Present address: School of Chemistry, Bedson Building, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK

Authors and Affiliations

  1. Molecular Photonics Laboratory, School of Chemistry, Bedson Building, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK

    Effat Bahaidarah, Anthony Harriman & Patrycja Stachelek

  2. Laboratoire de Chimie Organique et de Spectroscopies Avancées (ICPEES LCOSA), UMR 7515 CNRS, 25 rue Becquerel, 67087, Strasbourg Cedex 2, France

    Sandra Rihn, Elodie Heyer & Raymond Ziessel

Authors
  1. Effat Bahaidarah
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  2. Anthony Harriman
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  3. Patrycja Stachelek
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  4. Sandra Rihn
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  5. Elodie Heyer
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  6. Raymond Ziessel
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Corresponding author

Correspondence to Anthony Harriman.

Additional information

† Electronic supplementary information (ESI) available: Synthesis and characterization of PHEN1, PHEN2 and CORE, experimental and computational details, additional spectroscopic data, effect of temperature on ΦF and output from the quantum chemical calculations. See DOI: 10.1039/c4pp00204k

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Bahaidarah, E., Harriman, A., Stachelek, P. et al. Fluorescent molecular rotors based on the BODIPY motif: effect of remote substituents. Photochem Photobiol Sci 13, 1397–1401 (2014). https://doi.org/10.1039/c4pp00204k

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  • DOI: https://doi.org/10.1039/c4pp00204k

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